Graft polymers of low molecular weight styrene maleic anhydride resins and heterocyclic compounds and water soluble salts thereof

ABSTRACT

GRAFT POLYMERS OF LOW MOLECULAR WEIGHT STYRENE-MALEIC ANHYDRIDE RESINS WITH HETEROCYCLIC COMPOUNDS SUCH AS E-CAPROLACTAM, 2-PYRROLIDONE OR N-METHYL-2-PYRROLIDONE, AS WELL AS THE WATER-SOLUBLE ALKALI METAL OR AMMONIUM SALTS OF SAID GRAFT POLYMERS AND AQUEOUS SOLUTIONS OF SUCH SALTS ARE DISCLOSED. SUCH COMPOSITIONS ARE USEFUL, FOR EXAMPLE, IN FLOOR POLISH COMPOSITIONS.

United States Patent US. Cl. 260-285 R 3 Claims ABSTRACT OF THE DISCLOSURE Graft polymers of low molecular weight styrene-maleic anhydride resins with heterocyclic compounds such as e-caprolactam, 2-pyrrolidone or N-methyl 2 pyrrolidone, as well as the water-soluble alkali metal or ammonium salts of said graft polymers and aqueous solutions of such salts are disclosed. Such compositions are useful, for example, in floor polish compositions.

This invention relates to graft polymers of low molecular weight styrene-maleic anhydride resins with heterocyclic compounds such as e-caprolactam, 2-pyrrolidone and N-methybZ-pyrrolidone, as well as the water-soluble alkali metal or ammonium salts of said graft polymers and aqueous solution of such salts. Such compositions are useful, for example, as floor polish resins.

The reaction of styrene-maleic anhydride copolymers With heterocyclic compounds has been described in US. Pat. No. 3,136,738 to Hedrick et al. and in The Preparation and Properties of Grafts of Polycaprolactam on Vinyl Copolymers, C. B. Chapman and L. Valentine, Journal of Polymer Science, vol. XXXIV, pp. 3l9335 (1959). The graft polymers are described as soluble in m-cresol. It has now been discovered, however, that low molecular weight graft polymers of styrene-maleic anhydride copolymers with heterocyclic compounds such as e-caprolactam, 2-pyrrolidone, etc., can be prepared which in alkali metal or ammonium salt form are water-soluble.

The styrene maleic anhydride resin employed in this invention is relatively low in molecular weight, having about 1 to 5, preferably about 1 to 3, moles of styrene per mole of maleic anhydride and a molecular weight of about 400 to 5000, preferably about 1000 to 3000. The copolymer of styrene and maleic anhydride can be prepared by dissolving the styrene and maleic anhydride in a suitable solvent, employing as a polymerization catalyst a free-radical peroxide catalyst, preferably benzoyl peroxide or dicumyl peroxide, at temperatures of about 85 to 230 C. or higher. Suitable solvents include the aromatic hydrocarbon solvents, which can be either the active aromatic solvents, that is, containing an active hydrogen atom, such as cumene, pcymene, etc., or the non-active aromatics, such as xylene, toluene, etc. The active aromatic solvents are chain-terminating solvents and give lower molecular weight products. Other suitable solvents are the ketones, such as methylethylketone, which are also active solvents. The preferred manner of carrying out the polymerization is by what is known in the art as incremental feed addition. By this method the monomers and catalysts are first dissolved in a portion of the solvent in which the polymerization is to be conducted and the resulting solution fed in increments into a reactor containing solvent heated to reaction temperature, usually the reflux temperature of the mixture. When an aromatic solvent is employed as the solvent for the polymerization the formation of the copolymers causes a heterogeneous system, the polymer layer being the heavier layer and recoverable by merely decanting the upper aromatic solvent layer and drying. On the other hand, when a ketone is the solvent, the formed copolymer is usually soluble in the solvent media so that recovery of the products necessitates a solvent-stripping operation.

The styrene-maleic anhydride copolymers can be esterified e.g. about 50 to 100, preferably about 60 to 75, percent half-esterified with a water-soluble alcohol or capped glycol corresponding to the general formula:

wherein R and R are aliphatic hydrocarbon radicals, preferably saturated, of about 2 to 6 carbon atoms, and x:0 to about 10. The total number of carbon atoms in R and a single R is often less than about 7. Suitable alcohols and glycols for use in esterifying the styrene-maleic anhydride copolymer are, for example, n-propyl alcohol, ethyl alcohol, isopropyl alcohol, t-butyl alcohol, isoamyl alcohol, capped polyethylene glycols, e.g. polyethylene glycol monobutyl ether, and capped polypropylene glycols, etc. The esterified copolymers often have an acid number (determined as milligrams of KOH required to neutralize one gram of partially estcrified copolymer) of about to 325, preferably about to 250.

Esters of the styrene-maleic anhydride copolymer useful in the invention can be prepared by reacting the monohydric alcohol with the copolymer under either bulk or solvent conditions. The reaction temperature may vary depending upon whether a solvent is used, the styrene to maleic anhydride ratio in the copolymer, the particular alcohol employed, etc. Generally, esterification reaction temperatures of about 320 to 400 F., often about 340 to 360 F., can be employed. Advantageously, an esterification catallst such as lithium acetate can be employed.

The heterocyclic compounds employed in this invention are the cyclic amides having the general structure wherein n is 2 to 4 and non-deleterious substituents, e.g. lower alkyl groups, may be substituted on the ring. Suitabe compounds include e-caprolactam, Z-pyrrolidone and N-methyl-Z-pyrrolidone. The amount of cyclic amide employed in the graft polymers of this invention is that sufficient to provide a nitrogen content for said polymer of about 1 to 10 weight percent, preferably about 2 to 5 Weight percent, based on the total weight of the graft polymer.

It is thought that the reaction between the styrenemaleic anhydride resin and e-caprolactam proceeds to form a polyamide structure in addition to a polyimide structure due to the reaction with the styrene-maleic anhydride resin of e-aminocaproic acid formed by the reaction of e-caprolactam with water which is present in low concentrations in the reaction components. The reaction of the styrene-maleic anhydride resin with e-caprolactam could thus produce either or both imide and amide struc- Often preferred film-forming polymers are those pretures as follows: pared by addition polymerization of olefinically-unsatur rated monomers of 2 or 3 to about 12, preferably about -CHcH2 H 1CH-CH 4 to 8, carbon atoms. And, as stated above, preferably I 5 5 one or more of the monomers will be carboxyl groupcontaining. Suitable such polymers are disclosed, for example, in US. Pat. No. 2,754,280 to Brown et al., herein M incorporated by reference.

33:0 The polymerization systems most often employed to 1 produce the polymeric film-former used in 'the compo- NH 0 sition of the present invention are those systems wherein (CH,) h; OH addition polymerization (including coor interpolymerization) is effected in the presence of an emulsion polymerization catalyst, emulsifiers and water. These sys- L :L terns have the advantage of preparing an already emulsig fied polymeric film-former, which emulsion, after treat- 0: =0 ment, say, to remove or quench unexpired catalyst, may F'ifi be used directly in formulating the polish composition. NH Ordinarily, the film-forming polymers have a molecular Hs)5 v weight of about 10,000 to 50,000 and are preferably in 5 a finely-divided form, that is, characterized by a particle .|h (C 1): size in emulsion of about 0.02 to 1 micron, most prefer- L 4, ably about 0.04 to 0.6 micron. While the ratios of the various components in the polish compositions may vary widely, polymeric film-former will generally comprise about 50 to 90, often about 60 to 80, percent of the This structure was confirmed for this reaction product by infra red data which indicated the presence of a major imide peak and a minor amide peak. Data for the reactions of the styrene-maleic anhydride resin with 2-pyrcomposition, based on non-Volatile mafel'ials Y rolidone and with N-methyl-2-pyrrolidone are presented The Waxes that may be employed in the polish comin Table I. position of the present invention are emulsifiable, essen- TABLE I Wave length, it 6.05 5.87 6.1 5.75 5.85 5.61

Functional group Amlde Imide Amine... Ester--. Acid-. Anhydn'de. Styggne-maleic anhydride resin -Z-pyrrolidone Trace--. Major Low a not. Stryene-maleic anhydrlde resin -N-rnerhyl-Z- Major Maior Low.

pyrrolldone adduct.

1 A 70% half-esterified resin having a molar ratio of styrene to maleic anhydride of 2:1, the esterifying alcohol being n-propanol. I Only a trace quantity of the amide formation was shown tially hydrocarbonaceous waxes. They may be either to be present in the case of the 2-pyrrolidone adduct, crystalline or amorphous in structure and may be of while a major amide peak was reported in the case of the m e a animal Vegetable f g as Often P N-methyl-Z-pyrrolidone adduct. with no imide formation ferred, may be synthetically derived. The particular waxes reported fo this adduct, selected will depend on the physical properties desired in The floor polish compositions which incorporate the the PP emulsien- The Waxes Whleh e y graft polymers of this invention as the leveling resin comused {elllde, for p beeswax, OZOkeflte, 1111f;r ponent typically include, in addition, a polymeric film efystalllne a Paraffin f eamauba e former and a hydrocarbon wax. The graft polymers of ferfed Waxes Include emulslfiable, f y P y mate this invention are typically employed in such polish and T1315 Such as Polyethylene Wax FISheT'TI'OPSCh Waxesother aqueous compositions in an amount of about 0.5- The polyePhylene Waxes employed generally have a to 20, preferably about 10 to 20, weight percent of the leeulaf Welght of abou? 3000 to 15,090 y eopelymefs composition, based on non-volatile materials (NVM). of h l and addltlon pelymerlzablei P P The polymeric film-forming component in the improved containing monomers, e.g vinyl esters and acrylic acid composition of the present invention can be any of the esters, may also be P 1f desued- Advantageously, t emulsifiable, synthetic polymers conventionally employed hydrocarbon wax W111 also be a carboxyl group'contam in aqueous emulsion polish compositions. Such polymers mg carboxyla ted ,Waxes are well known and are include those obtained by addition polymerization of often derived by oxldatlon of h hydrocarbon for vinyl monomers, e.g., styrene, methyl styrene, divinyleXPmPIe polyethsfhme 013,111 case of Waxes benzene and other vinyl aromatics, acrylic acids and estamed h ahdmon Polymenzahoh of olefin: h ters, substituted acrylic acids and esters, vinyl halides, mershby mclhsloh of Ihlhor amohhts h copolymehzahl? vinyl esters, etc. Examples of suitable film-formers inolhhhlcahy'hhshthrhted carhoxyhc aclds h as hcryhc elude polystyrene, styrene-acrylic acid copolymers, ethylacld lheihacryhc hold In the polymenzahoh h h acrylate-acrylic acid copolymers, ethylacrylate-methacryl- E It often g h that hg ggohp'cfohtallhlhg ic acid copolymers, styrene-methacrylic acid copolymers, y meat on waxes avlhg an er 0 at east I about 5 be employed. Examples of suitable synthetic Preferably the hhh former hke the levehng waxes and method of preparing same are those disclosed,

resin, be a carboxyl group-containing polymer such as thhse.comphsed.of polymerized acrylic acid methacryhc z ah d lhlhh l z ts? 221 2 ?h2 3 i fg h r hzhli held hachmc held Advahtageouhy about 1 to herein incorporated by reierence. Generally, the hydro of the monomer hhlts m the hhh'fohhmg polymer will he carbon wax will comprise about 1 to 20, preferably about earboxy1 groupjcontaining monomer units and often 3 to 15, weight percent of the polish composition, based about 2 to 7% will contain carboxyl groups. By the expreson l tfl materials.

sion car y E P P as used herein and in h elalfns A novel aspect of the floor polish compositions of is mea t u s lfi cal'boxyllc acid p Including this invention is that the polishes exhibit an unusually carboxylic i ps which v e e ra iz d to long drying time. This feature can be utilized to achieve their salt forms. improved flow and leveling characteristics, particularly 5 under high temperature or low humidity conditions; or when the polish is applied over a porous substrate, such as aged and worn tile.

A unique application for the graft polymers of this invention is the use of such polymers as a one-component floor polish. In such a floor polish composition the graft polymer of styrene-maleic anhydride with the cyclic amide is employed to fulfill the performance requirements of polymeric film-former, leveling resin and hydrocarbon wax. In addition to ease of formulation, the one-component polishes of this invention may be prepared as water clear solutions, whereas most present day emulsion products have a milky, opaque solution appearance. In these one-component polishes, a major amount of water is employed with a minor amount of the graft polymer of the present invention. Generally a solution containing In preparing the graft polymers, some reactions were conducted employing a fusion or hot melt technique while a common solvent medium was employed in other reactions. The only noticeable difference in the product obtained was an improved resin color where the solvent technique was employed. The reactants generally were heated to temperatures in the range of 140 to 175 C. for a period of five to seven hours. Where the fusion process was employed, the product was isolated by repeated waterwashing. Where the common solvent method was employed, the product was separated by precipitation with a non-solvent such as pentane or hexane. Table II lists various graft polymers of this invention with corresponding analytical data.

TABLE II.SYNTHESIS OF STYRENE MALEIC ANHYDRIDE RESIN ADDUCTS A B C D E F G Styrene-maleic anhydride resin Resin 1 1 Resin 1 Resin 2 2 Resin 3 8 Resin 1 Resin 1 Resin 1 Resin charged, grams. 100 635 1 1 100 100. 100 100. Coreactant- 2-pyrol 2-pyrnl 2-pyr 2-pyr m-Pyrol NMeoli v-Pyrol ,v

Py Coreactant charged, rams 105 635 101 100 120 60 100. Catalyst- HBZ HBZ HBZ HBZ HBZ HBZ HBZ. Catalyst grams-.- 1.0- 13.0.- 2.0- 2.0 1.0 0.80 1,0, Accelerator- Accelerator charged, grams. Solvent charged- Solvent charged, gram Reaction time (hours) 6.0- 5.5- 6.0- 6.0. 5.0- 5.0- 5.0. Reaction temperature C.).- 175.. 175 175 175 150 165. Appearance of unwashed product.. Dark viscous Dark viscous Dark viscous Dark viscous Dark viscous Dark viscous Dark viscous liquid. liquid. liquid. liquid. liquid. liquid. li uid. Physical properties of washed produc s:

Acid Number 123.- 109 192 169 172 170 r 130. Percent nitrog n 2.82. 3.73. 3.20. 1.81 2.57 4.33 2,39, Melting point (cap).- 108-1 98-110 55-7 118-138 90-110 6781 95430, Iodine No--- 1.2- 4.9- 4.0- 3.6- 0.6- 2.4- 19.5. Solution color (15% NVR). 7 5 7 7 7 5 9-10, Sc ubability using 1.5% Spic and pan:

Film pp r n Cr k Cr Cracked Cracked Cracked Exc. gloss..-.. Cracked. Blush 100 100. 25 70 100 10 50, 25% remov 400 400 40 400 400 10 2Q. 50% remov 500 500 50 500 500 30. 100% remov l +500 +500 7 +500 +500 60,

H I J K L M Styrene-maleic anhydride resin Resin 1 Resin 1 Resin 1 Resin 4 4 Resin 5 I Resin 5 Resin charged, grams 300 30 100 200..- 200 300, Core'actant Caprolactam.... Caprolac m Capr Caprolactarn Caprolactmn capmiactam, Coreactant charged, grams. 63 300 100 72 85 Y 255. Catalyst Catalyst- HBZ N HBZ Catalyst charged, grams- 2.0. 12.0. 0.20. 1.3 Accelerator- Water- N-acetyl caprolactam. Accelerator charged, grams- 30.0. 0.23. Solvent charged- MIAK Solvent charged, grams- 150 Reaction time (hours) 3.0. 5.0. 6.0- 3.0. 2.5- 3,0, Reaction temp. 0.). 16 450 150. 180.... 150 15 Appearance of unwashed product...-- Viscous liquid... Dark liq id..- Dark liquid Di]? viscous Dark solid Dark solid,

qui Physical properties of washed products:

Acid Number (TB C) 174 14 233 283 172, Nitrogen- 2.15- 2.75 2.52- 3.02- 6.7. Melting Point (cap) 91-115 77-118 103-126 75-98 -34. Iodine No 3.7- 7.2- 3.6- 0.5- 1.8 Solution Color (15% NVR) 1- 4 7 5 6 Segubability using 1.5% Spic and pan:

Film Appearance Cracked Cracked Very slight crack Crack Exc. gloss Rlnsh 50 10 10 5-10 an 25% Removal 20 20 100 10 10 50% Removal.- +200 15 15 100% Removal 50 +200 20 20' 1 Molar ratio of styrene to maleic anhydride=2:1; percent half-esterified with n-propanol.

2 Molar ratio of styrene to maleic anhydride=1:l; molecular weight=1600. 3 Molar ratio of styrene to maleic anhydride=3:l; molecular weight=1900. l Molar ratio of styrene to maleic anhydride=3:1; molecular weight=1700.

5 Molar ratio of styrene to maleic anhydride=1z 1; molecular weight=600700.

i 2-Pyrrolidone.

1 N-methyl2-pyrrolidone.

8 N-methylol-2-pyrrolidone. 9 N-vinyl-2-pyrrolidone.

Benzoie acid.

Methyl isoamyl ketone.

about 0.5 to 25, preferably about 12 to 20, weight percent graft polymer provides a workable system.

tions of this invention:

The following example is illustrative of the composi- The styrene-maleic anhydride resin, the cyclic amide compound and the catalyst were charged to a flask fitted Resin-adduct H from Table II in the amount of 30 grams was solubilized in grams water using ammonium hydroxide to aid in dissolving the polymer. The resulting solution comprised 16.1 weight percent resin solids with pH=9.2. This solution was applied at the rate of 526 ftF/gal. to a tile floor to produce a high gloss coating.

A solution of 16 grams resin-adduct M in 85 grams water and 1.5 ml. 28 percent solution of ammonium hydroxide was prepared-The solution comprised 15.3 weight percent solids with pH=9.0. The solution produced a high gloss coating when applied to a.tile floor at the rate Table III illustrates the results obtained from employing'the resin-adducts of Table II in floor polish compositions. The polishes were applied at 526 ftP/gal. spreading rate and scrubbed with 1.5% Spic and Span solution using the Gardner Washability Machine. The polish compositions employed in Table III have the following formulations.

Polish No. 1: Volume percent r RWL-lOO-LC, a commercial polystyrene emulsion, percent solids by weight 65.0

Leveling resin, 15 percent solids by weight,

NH, soln. in water 12.5 U-3050, a commercial acrylate ester emulsion,

15 percent solids by weight 12.5 AC-680, a commercial polyethylene wax emulsion, 15 percent solids by weight 10.0 KP-140, a commercial tri-butoxyethyl phosphate 1.0 2-pyrrolidone 0.4 0

Polish No. 2:

Rhoplex B-23l, a commercial polyacrylate emulsion, 15 percent solids by weight 65.0 Leveling resin, 15 percent solids by weight,

NH, soln. in water 25.0 AC-680 10.0

KP-14-0 1.2 2-pyrrolidone 0.5

Polish No. 3:

NH-401-DL, a commercial polyacrylate emulsion, 15 percent solids by weight 65.0 Leveling resin, 15 percent solids by weight,

NH, soln. in water 25.0 AC-680 10.0 KP-140 1.2 2-pyrrolidone 0.5 Ethylene glycol 2.0

Polish No. 4:

Rhoplex B336, a commercial polyacrylate emulsion, 15 percent solids by weight 72.5 Leveling resin, 15 percent soldis by weight,

NH, soln. in water 16.5 AC-680 11.5 Carbitol, a commercial diethylene glycol monoethyl ether 1.5 Ethylene glycol 1.5 KP-140 0.35 FC-128 (1% soln.), a commercial fluorochemical surfactant 0.4

TABLE III.PERFORMANCE 0F RESIN ADDUCTS IN FLOOR POLISH COMPOSITIONS Resin- Resinadduct adduct Resin Leveling resin- A1 E 2 1 9 Polish No. 1:

Film appearanee- Excellent Excellent Excellent Strokes to blush 10 10 10 50% removal. +400 300 50 100% removal +400 +400 100 Polish No. 2:

Film appearance Excellent Excellent Excellent Strokes to blush 60 60 10 100 so 20 +300 100 30 Polish No. 3:

Film appeanace Excellent Excellent Excellent Strokes to blush 200 100 30 50% removal. +500 +500 100 100% removal- +500 +500 200 Polish No. 4:

Film appeaanee Excellent Excellent Excellent Strokes to blush 100 100 30 50% removal +500 +500 300 100% removal- +500 +500 +500 1 See resin-adduet ,A" in Table I. 2 See resin-adduct E in Table I.

a See footnote (1) bottom of Table I.

TABLE IV.ONECOMPONENT POLISHES Polish No. 1 Polish No. 2 Polish No. 3

Styrene-malcic an- Resin 1 Resin 1 with Resin 1 with 2- hydride resin adduct. 2-pyrpyrrolidonc.

rolidone.

Plastlclzer 0.15% KP- 0.15% KP-140,

140, 0.20% 0.20% carbito carbltol.

Film appearance 526 Continuous; Cracked Continuous;

ftJ/gal. slight slight cratering. cratcring. 1,600-2,O00ft. Igal Continuous Cracked Continuous.

Blush resistance 3 l5 00 Strokes for 25% film removal 1 See footnote (1) bottom of Table II. 2 Weight percent based on weight of the resin solution. 3 N umber of strokes required for appearance. 4 Films applied at 526 ti/gal, spreading rate and scrubbed with'1.5% Spic and Span solution using Gardner Washability Machine.

It is claimed: 1. A detergent resistant aqueous emulsion polish composition comprising a polymeric film-former, a carboxyl group-containing leveling resin and a hydrocarbon wax, the improvement comprising the employment as the car'- boxyl group-containing leveling resin of a water soluble, ammonium or alkali metal salt of a graft polymer of a styrene-maleic anhydride copolymer having about a 1:1 to 5:1 molar ratio of styrene to maleic anhydride and a molecular weight of about 400 to 5,000, with a heterocyclic compound having the structure:

wherein R and R are aliphatic hydrocarbon radicals of about 2 to 6 carbon atoms, the total number of carbon atoms in R and a single R is less than about 7, and x is 0 to about 10. I

3. The polish of claim 1 in which the heterocyclic compound is selected from the group consisting of e-caprolactam, 2-pyrrolidone and N-methyl-Z-pyrrolidone' References Cited UNITED STATES PATENTS 2,586,477 2/1952 Niles '26078.j5 T 2,607,762 8/1952 Bowen--. 260-78.5'I 2,757,715 7/1956 Bowen 260 -78.5 T 3,136,738 6/1964 Hedrick 260-857 G 3,234,158 2/1966 Pfiuger 26028.5 3,313,755 4/1967 a ORourke 260- -28.5 ALLAN LIEBERMAN, Primary Examiner S. L. FOX, Assistant Examiner U.S. Cl. X.R.

260-285 A, 28.5 D, 29.6 HN 

